Synergistic fungicide and/or bactericide composition

ABSTRACT

The invention concerns a synergistic fungicide and/or bactericide composition comprising dodine and a derivative of the anilino-pyrimidine family. The invention also concerns a preventive or curative method for fighting against phytopathogenic fungi and/or bacteria using such a composition.

this application is a 371 of PCT/FR99/00845, filed Sep. 12, 1999.

The present invention relates to a synergistic fungicidal and/orbactericidal composition comprising dodine and a compound of theanilino-pyrimidine family, and to a method of using this composition forthe curative or preventative protection of crops against fungal attack.

It is always desirable to improve the range of activity and efficacy ofsuch fungicidally active compounds, or to make them more potent bycombining them with other molecules in order to obtain an improvedproduct or else to prevent the appearance of fungal strains which areresistant.

Equally, it is very desirable to have available fungicidal productswhich have an improved duration of action so that the number of plantprotection treatments required for good control of the parasites can bespaced out over the course of time.

In any case, it is particularly advantageous to be able to reduce thequantity of chemical products sprayed in the environment whileguaranteeing effective protection of the crops against fungal attack.

It has now been found that one (or more) of the above aims can beachieved by the fungicidal and/or bactericidal composition according tothe present invention.

The present invention primarily therefore relates to a synergisticfungicidal and/or bactericidal composition comprising, as compound A,dodine, which is also known as dodecylguanidine monoacetate, and atleast one fungicidal compound B selected from the group comprising acompound of the anilino-pyrimidine family, that is to say B is chosenfrom the group comprising cyprodinil, pyrimethanil or mepanipyrim.

The fungicidal and/or bactericidal composition according to theinvention advantageously comprises the components A and B in a weightratio A/B of between 1/26 and 160/1, preferably between 1/4 and 60/1,especially advantageously in a ratio of between 3/8 and 9/1.

Naturally, this fungicidal and/or bactericidal composition can contain asingle compound B or more than one such compound, for example, 1, 2 or 3compounds B, depending on the intended use.

Amongst the more particularly preferred meanings of the above-definedcompound B, pyrimethanil is especially preferred. Quite unexpectedly,the composition according to the invention improves in a remarkablemanner the activity of active materials taken separately for a number offungi which are particularly harmful to crops, such as, in particular,grapevine or the potato family. This improvement manifests itselfespecially by a reduced dosage of each of the constituents, which isparticularly advantageous for the user and the environment. Thefungicidal and/or bactericidal product (mixture) thus exhibitssynergistic properties which are borne out by applying the methoddefined by Limpel L. E., P. H. Schuldt and D. Lammont, 1962, Proc. NEWCC16:48-53, using the following formula, also called Colby formula:

E=X+Y−X.Y/100

in which:

E is the expected percentage of inhibition of the growth of the fungusby a mixture of the two fungicides A and B at defined doses,respectively equal to a and b;

X is the observed percentage of inhibition by the fungicide and/orbactericide A at the dose a,

Y is the observed percentage of inhibition by the fungicide and/orbactericide B at the dose b. When the observed percentage of inhibitionfor the mixture is greater than E, there is synergism.

When component B is pyrimethanil, the ratio A/B is preferably between1/4 and 60/1, this ratio especially advantageously being between 3/8 and9/1, this ratio most preferably being 3/1 for all of the crops underconsideration.

The structures which correspond to the common names of the activematerials A and B are given in at least one of the 2 following works:

“The pesticide manual”, edited by Clive TOMLIN, and published by theBritish Crop Protection Council, 11th Edition, 1997 (pages 451, 1068,319 and 784);

The “Index phytosanitaire 1998”, edited by the Association deCoordination Technique Agricole, 34th Edition.

The fungicidal and/or bactericidal composition according to theinvention comprises, as active material, a compound A and at least onecompound B as a mixture with solid or liquid agriculturally acceptablecarriers and/or surfactants which are also agriculturally acceptable.Substances which can be used in particular are the usual inert carriersand the usual surfactants. These compositions extend not only tocompositions which are ready to be applied to the crop to be treated bymeans of a suitable device, such as a sprayer, but also to concentratedcommercial compositions which must be diluted before being applied tothe crop. By active material there is to be understood the combinationof at least one compound A with at least one compound B.

These compositions can also contain any type of other ingredients suchas, for example, protective colloids, adhesives, thickeners,thixotropes, penetrants, stabilizers, sequestering agents and the like.More generally, the compounds A and B can be combined with all solid orliquid additives which are conventionally used in the art offormulation.

Generally speaking, the compositions according to the invention usuallycontain from 0.05 to 95% (by weight) of active material, one or moreliquid or solid carriers and, if appropriate, one or more surfactants.

The term “carrier” is to be understood as meaning in the present text anatural or synthetic organic or mineral material with which the activematerial is combined to facilitate its application to the aerial partsof the plant. This carrier is thus generally inert and must beagriculturally acceptable, especially by the treated plant. The carriermay be solid (clays, natural or synthetic silicates, silica, resins,waxes, solid fertilizers and the like) or liquid (water, alcohols,especially butanol, and the like).

The surfactant may be an ionic or nonionic emulsifier, dispersant orwetter, or a mixture of such surfactants. By way of example there may bementioned salts of polyacrylic acids, of lignosulphonic acids, ofphenolsulphonic acids or of naphthalenesulphonic acids, polycondensatesof ethylene oxide and fatty alcohols or fatty acids or fatty amines,substituted phenols (especially alkylphenols or arylphenols), salts ofsulphosuccinic esters, taurine derivatives (especially alkyl taurates),phosphoric esters of alcohols or of polyoxyethylated phenols, esters offatty acids and polyols, and derivatives of the above compounds whichhave a sulphate, sulphonate and phosphate function. The presence of atleast one surfactant is generally indispensable when the active materialand/or the inert carrier are not soluble in water and when theapplication vehicle is water.

The compositions according to the invention for use in agriculture cantherefore contain the active material within very wide limits of from0.05% to 95% (by weight). Their surfactant content is advantageouslybetween 5% and 40% by weight. Unless otherwise specified, thepercentages given in the present description including the claims are byweight.

These compositions according to the invention, themselves, come in awide variety of solid or liquid forms.

As solid forms of compositions there may be mentioned powders fordusting (whose active material content may be as high as 100%) andgranules, especially those obtained by extrusion, by compacting, byimpregnating a granulated carrier, by granulation of a powder (theactive material content in these granules being between 0.5 and 80% inthe last-mentioned cases), tablets or effervescent tablets.

The fungicidal and/or bactericidal composition according to theinvention may also be used in the form of powders for dusting; acomposition comprising 50 g of active material and 950 g of talc mayalso be used; a composition comprising 20 g of active material, 10 g offinely divided silica and 970 g of talc may also be used; theseconstituents are mixed and ground, and the mixture is applied bydusting.

As liquid forms of compositions, or forms intended to give liquidcompositions upon application, there may be mentioned solutions, inparticular water-soluble concentrates, emulsions, concentratedsuspensions, aerosols, wettable powders (or sprayable powders), pastes,and gels.

Concentrated suspensions which can be applied by spraying are preparedin such a way that a stable fluid product is obtained which does notsettle, and they usually contain 10 to 75% of active material, 0.5 to15% of surfactants, 0.1 to 10% of thixotropes, 0 to 10% of suitableadditives such as antifoams, corrosion inhibitors, stabilizers,penetrants and adhesives, and, as carrier, water or an organic liquid inwhich the active material is sparingly, or not, soluble: certain organicsolid materials or mineral salts may be dissolved in the carrier to helpprevent settling, or as antifreeze agents for the water.

By way of example there is now given a composition of a concentratedsuspension:

Example SC 1: active material 500 g polyethoxylated tristyrylphenolphosphate 50 g polyethoxylated alkylphenol 50 g sodium polycarboxylate20 g ethylene glycol 50 g organopolysiloxane oil (antifoam) 1 gpolysaccharide 1.5 g water 316.5 g

Wettable powders (or sprayable powders) are usually prepared in such away that they contain 20 to 95% of active material; they usuallycontain, in addition to the solid carrier, 0 to 30% of a wetter, 3 to20% of a dispersant, and, if necessary, 0.1 to 10% of one or morestabilizers and/or other additives, such as penetrants, adhesives,anticaking agents, colorants and the like.

To obtain sprayable powders, or wettable powders, the active materialsare mixed intimately with the additives in suitable mixers and themixtures are ground in mills or other suitable grinders. This givessprayable powders with advantageous wetting and suspending properties;they can be suspended in water to give any desired concentration, andthese suspensions are very advantageously suitable for foliarapplication to the plants, in particular.

Instead of wettable powders, pastes may be made. The conditions andmodes of making and using these pastes are similar to those for wettablepowders or sprayable powders.

By way of example there are now given various compositions of wettablepowders (or sprayable powders):

Example WP 1: active material 50% ethoxylated fatty alcohol (wetter)2.5% ethoxylated phenylethylphenol (dispersant) 5% chalk (inert carrier)42.5% Example WP 2: active material 10% branched syntheticC13-oxoalcohol 0.75% ethoxylated with 8 to 10 ethylene oxide units(wetter) neutral calcium lignosulphonate (dispersant) 12% calciumcarbonate (inert filler) to 100% Example WP 3: This wettable powdercontains the same ingredients as in the preceding example, but in thefollowing proportions: active material 75% wetter 1.50% dispersant 8%calcium carbonate (inert filler) to 100% Example WP 4: active material90% ethoxylated fatty alcohol (wetter) 4% ethoxylated phenylethylphenol(dispersant) 6% Example WP 5: active material 50% mixture of anionic andnonionic 2.5% surfactants (wetter) sodium lignosulphonate (dispersant)5% kaolin type clay (inert carrier) 42.5%

The aqueous dispersions and emulsions, for example the compositionsobtained by diluting a wettable powder or an emulsifiable concentrateaccording to the invention with the aid of water, come within thegeneral scope of the present invention. The emulsions may be of thewater-in-oil type or the oil-in-water type and they can have a thickconsistency, such as that of a “mayonnaise”.

The fungicidal compositions according to the invention may be formulatedin the form of water-dispersible granules, which equally come within thescope of the invention.

These dispersible granules, whose apparent density is generally betweenapproximately 0.3 and 0.6, have a particle size of generally betweenapproximately 150 and 2000, preferably between 300 and 1500, microns.

The active material content of these granules is generally betweenapproximately 1% and 90%, preferably between 25% and 90%.

The remainder of these granules is essentially composed of a solidfiller and, if appropriate, surface-active adjuvants which impart, tothe granules, properties of dispersibility in water. These granules canessentially belong to two different types, depending on whether theirfiller is water-soluble or not. When the filler is soluble in water, itmay be mineral or, preferably, organic. Outstanding results wereobtained with urea. An insoluble filler is preferably mineral, such as,for example, kaolin or bentonite. It is advantageously accompanied bysurfactants (in a proportion of 2 to 20% by weight of the granules) ofwhich more than half is composed of, for example, at least oneessentially anionic dispersant, such as an alkali metal or alkalineearth metal polynaphthalenesulphonate, or an alkali metal or alkalineearth metal lignosulphonate, the remainder being composed of nonionic oranionic wetters, such as an alkali metal or alkaline earth metalalkylnaphthalenesulphonate.

In addition, other adjuvants such as antifoams may be added, even thoughthis is not compulsory.

The granules according to the invention can be prepared by mixing thenecessary ingredients and then granulating the mixture by varioustechniques known per se (granulator, fluidized bed, atomizer, extrusionand the like). This generally ends with crushing followed by screeningto the selected particle size within the abovementioned limits. Granulesobtained as above and then impregnated with a composition which containsthe active material may also be used.

It is preferably obtained by extrusion, the procedure being as indicatedin the examples hereinbelow.

EXAMPLE DG1

Dispersible Granules

In a mixer, 90% by weight of active material and 10% of urea beads aremixed. The mixture is subsequently ground in a pin mill. This gives apowder which is moistened with approximately 8% by weight of water. Themoist powder is extruded in a perforated-roll extruder. This givesgranules which are dried and then crushed and screened to giverespectively only those granules which have a size of between 150 and2000 microns.

EXAMPLE DG2

Dispersible Granules

The following constituents are mixed in a mixer:

active material 75% wetter (sodium alkylnaphthalenesulphonate)  2%dispersant (sodium polynaphthalenesulphonate)  8% inert water insolublefiller (kaolin) 15%

This mixture is granulated in a fluidized bed in the presence of waterand then dried, crushed and screened to give granules of a size between0.15 and 0.80 mm.

These granules can be used alone, as a solution or as a dispersion inwater so as to obtain the desired dose. They can also be used forpreparing combinations with other active materials, especiallyfungicides, the latter being in the form of wettable powders or ofgranules or aqueous suspensions.

Those compositions which are designed to be suitable for storage andtransport contain more advantageously 0.5 to 95% (by weight) of activematerial.

The invention furthermore relates to a method for the curative orpreventative control of crop-phytopathogenic fungi and/or bacteria,characterized in that an effective, non-phytotoxic quantity of acombination of compound A and at least one compound B is applied to theaerial parts of the plants, for example in a fungicidal and/orbactericidal composition according to the invention.

The crop-phytopathogenic fungi which can be controlled by this methodare especially the following:

from the group of the Oomycetes:

those of the genus Phytophthora, such as Phytophthora phaseoli,Phytophthora citrophthora, Phytophthora capsici, Phytophthora cactorum,Phytophthora palmivora, Phytophthora cinnamoni, Phytophthora megasperma,Phytophthora parasitica, Phytophthora fragariae, Phytophthora cryptogea,Phytophthora porri, Phytophthora nicotianae, Phytophthora infestans(solanum blight, especially potato or tomato blight);

from the family of the Peronosporaceae, in particular Plasmoparaviticola (grapevine downy mildew), Plasmopara halstedei (sunflower downymildew), Pseudoperonospora sp. (in particular cucurbit downy mildew(Pseudoperonospora cubensis) and hop downy mildew (Pseudoperonosporahumuli)), Bremia lactucae (lettuce downy mildew), Peronospora tabacinae(tobacco blue mould), Peronospora destructor (onion downy mildew),Peronospora parasitica (brassica downy mildew), Peronospora farinosa(endive mildew and beet mildew),

from the group of the Adelomycetes (ascomycetes):

those of the genus Alternaria, for example Alternaria solani (solanumearly blight, especially tomato and potato early blight) Alternariaporri (pear tree early blight), Alternaria mali (apple tree earlyblight),

those of the genus Guignardia, especially Guignardia bidwellii (grapeblack rot),

those of the genus Venturia, for example Venturia inaequalis, Venturiapirina (apple or pear scab),

those of the genus Oidium, for example vine powdery mildew (Uncinulanecator); powdery mildew of vegetable crops, for example Erysiphepolygoni (powdery mildew of crucifers); Leveillula taurica, Erysiphecichoracearum, Sphaerotheca fuligena (powdery mildew of Cucurbitaceae,of Compositae, of tomato); Erysiphe conmmunis (cabbage powdery mildew);Erysiphe pisi (powdery mildew of the pea or of the lucerne); Erysiphepolyphaga (powdery mildew of the haricot bean and of the cucumber);Erysiphe unbelliferarum (powdery mildew of umbellifers in particular ofthe carrot); Sphaerotheca humuli (hop powdery mildew),

those of the genus Taphrina, for example Taphrina deformans (peach leafcurl),

those of the genus Botrytis cinerea (vine, vegetable and market gardencrop, arboriculture, pea, and the like),

those of the genus Phomopsis viticola (vine excoriosis),

from the group of the Basidiomycetes:

from the Rhizoctonia spp family, for example Rhizoctonia solani.

Diseases of bacterial and viral origin which can be controlled by thismethod are in particular

fire blight, Erwinia amylovora;

bacterial spot of stone fruits, Xanthomonas campestris;

pear bacterial canker, Pseudomonas syringae.

The crops under consideration for the purposes of the present inventionare preferably vegetable crops (beans, onions, cucurbits, cabbage,potatoes, tomatoes, capsicums, spinach, peas, lettuce, celery, endives),fruit crops (strawberry plants, raspberry plants), arboricultural crops(apple trees, pear trees, cherry trees, ginseng, lemon trees, coconutpalms, pecan trees, cacao trees, nut trees, hevea trees, olive trees,poplars, banana plants), grapevines, tobacco and ornamentals.

A classification neither by fungi nor by bacteria aimed at, but bytarget crops, can be illustrated as below:

grapevine: oidium (Uncinula necator), downy mildew (Plasmoparaviticola), rot (Botrytis cinerea), excoriosis (Phomopsis viticola) andblack rot (Guignardia bidwellii),

Solanaceae: mildew (Phytophthora infestans), blight (Alternaria solani)and rot (Botrytis cinerea),

vegetable crops: downy mildews (Peronospora Sp., Bremia lactucae,Pseudoperonospora sp.), blight (Alternaria sp.), rot (Botrytis cinerea),root rot (Rhizoctonia spp.), oidium (Erysiphe sp.: Sphaerothecafulginea).

arboriculture: scab (Venturia inaequalis, V. pirina), bacterial diseases(Erwinia amiylovora, Xanthomonas campestris, Pseudomonas syringae),oidium (Podosphaera leucotricha) and brown rot (Monilia fructigena),botrytis.

citrus fruit: scab (Elsinoe fawcetti), melanose (Phomopsis citri) anddiseases caused by Phytophthora sp.

The fungicidal and/or bactericidal composition of the invention isapplied by means of various treatment methods, such as:

spraying a liquid comprising said composition onto the aerial parts ofthe crops to be treated,

dusting, incorporation of granules or powders into the soil, pouring,injection into trees, or painting on.

The preferred treatment method is spraying a liquid onto the aerialparts of the crops to be treated.

“Effective, non-phytotoxic quantity” is to be understood as meaning-suchan amount of composition according to the invention to allow fungi andbacteria which are present or likely to appear on the crops to becontrolled or destroyed while avoiding any notable symptoms ofphytotoxicity on said crops. Such a quantity is likely to vary withinwide limits, depending on the fungus or the bacterium to be controlled,the type of crop, the climatic conditions, and the compounds in thefungicidal and/or bactericidal composition according to the invention.This quantity can be determined by systematic field trials known to theskilled worker.

When making use of the method according to the invention, the useconcentrations will generally be in this case by foliar treatment ongrapevine, vegetable crops, arboriculture, citrus fruit and the like:

25 to 4000 g/ha of compound B, for example pyrimethanil, +150 to 4000g/ha of compound A and more precisely 50 to 1000 g/ha+250 to 3000 g/ha,that is to say a total dose of composition according to the invention ofbetween 175 to 8000 g/ha, preferably between 300 and 4000 g/ha. 100 to800 g/ha of compound B and 300 to 900 g/ha of compound A are preferablyused, that is to say a total dose of composition according to theinvention of between 400 g/ha and 1700 g/ha.

Most advantageously, 501 g/ha of compound A+167 g/ha of compound B(ratio 3/1), that is to say 668 g/ha in total, will be used.

Finally, the invention relates to a product comprising at least onecompound A and at least one compound B for controlling phytopathogenicfungi and/or bacteria in an environment by simultaneous, sequential orseparate application.

The example which follows is given purely by way of illustrating theinvention which is limited thereby in no way whatsoever.

Example: Combination of pyrimethanil and dodine in controlling applescab

The fungicides evaluated are the following:

EXP A: SC formulation containing 400 g of dodine/1, Scala ® Scformulation containing 400 g of pyrimethanil/l.

The fungicidal compositions evaluated are the following:

EXPA at the doses of 150-300 and 600 g of dodine/ha, Scala ® at thedoses of 50-100 and 200 g of pyrimethanil/ha, EXPA + Scala ® at the doesof 150 + 50 − 300 + 100 and 600 + 200 g of dodine + pyrimethanil/ha.

Apple plants (var. Melrose Golden) at the 5-6-leaf stage are inoculatedwith an aqueous suspension containing 150 000 spores of Venturiainaequalis/ml of inoculum. The plants are then placed in a climatic cellat 16-18° C., 100% RH (relative humidity) for 3 days. They are thentreated with the fungicidal compositions at the doses cited above (12repeats/dose) in a plant protection mixture at 500 l/ha and are againplaced under the conditions described above. One month after theinoculation, scores are awarded. This consists in estimating thediseased leaf surface area in the two leaf stages sensitive to thedisease and, by comparing with an untreated contaminated control, indefining the percentage efficacy according to the following formula:

% practical efficacy=100×(% contamination Control−% contaminationTrial)/% contamination Control

The theoretical efficacy according to the Colby formula is calculatedbased on the following formula:

% theoretical efficacy A+B=% practical eff. A+% practical eff. B−(%practical eff. A×% practical eff. B/100)

III: Results

dodine/ pyrimethanil 0 g/ha 50 100 200 Practical efficacy  0 g/ha 0 65.465.4 61.5 150 30.8 84.6 300 76.9 92.3 600 75 90.4 Theoretical efficacy(Colby):  0 g/ha 0 65.4 65.4 61.5 150 30.8 76.06 300 76.9 92.01 600 7590.38 Synergism:  0 g/ha 150 9 300 0 600 0

Pyrimethanil and dodine offer partial protection when they are usedalone. The combination in the ratio dodine/pyrimethanil=3/1 generates ahigh level of protection for doses of between 150+50 and 600+200 g/ha.

A certain synergistic relationship is obtained at the 150+50 g/ha dose(+9% efficacy).

What is claimed is:
 1. A synergistic fungicidal composition comprising,as compound A, dodine and at least one fungicidal compound B selectedfrom the group consisting of cyprodinil, pyrimethanil and mepanipyrim;said composition comprising the components A and B in a weight ratio A/Bof between 1/26 and 160/1.
 2. The composition of claim 1, wherein saidcompound B is pyrimethanil.
 3. The composition of claim 1, wherein theratio A/B is between 1/4 and 60/1.
 4. The composition of claim 1,wherein the compounds A and B are mixed with solid or liquidagriculturally acceptable carriers.
 5. The composition of claim 1,wherein the amount of compounds A and B are from 0.05 to 95% (byweight).
 6. The composition of claim 1, wherein the components A and Bhave a weight ratio A/B between 3/8 and 9/1.
 7. The composition of claim1, wherein the components A and B have a weight ratio A/B of 3/1.
 8. Thecomposition of claim 1, wherein the compounds A and B are mixed withagriculturally acceptable surfactants.
 9. A method of controllingphytopathogenic fungi or bacteria in an environment, comprising applyingantifungal or antibacterial effective, but non-phytotoxic amount of thecomposition of claim 1 to said environment.
 10. A method for thecurative or preventative control of crop-phytopathogenic fungi orbacteria on a plant, comprising applying to the aerial parts of theplant an antifungal or antibacterial effective, but non-phytotoxicquantity of the composition of claim
 1. 11. The method of claim 10wherein the composition of claim 1 is liquid and the application saidcomposition is carried out by spraying.
 12. The method of claim 11,wherein said composition has a dose of between 175 and 8000 g/ha and isapplied for foliar treatment.
 13. The method of claim 12, wherein saidcomposition has a dose of between 400 and 1700 g/ha.
 14. The method ofclaim 12, wherein said composition has a dose of between 300 and 4000g/ha.
 15. The method of claim 13, wherein said composition has a dose of668 g/ha.